Solid state polymerization process for foamed poly(ethylene naphthalate)

ABSTRACT

This invention includes a process for preparing a solid state polymerized poly(ethylene naphthalate) or PEN polymer comprising: (1) preparing a molten PEN polymer with an intrinsic viscosity of from about 0.25 dl/g to about 0.55 dl/g, (2) dispersing an inert gas into the molten PEN polymer to form a foamed PEN polymer with a void fraction of from about 0.10 to about 0.50, (3) forming the foamed PEN polymer into granules, (4) devolatilizing the granular PEN polymer at a temperature of from about 80° C. to about 140° C., (5) crystallizing the devolatilized PEN polymer at a temperature of from about 150° C. to about 260° C., and (6) solid state polymerizing the crystallized PEN polymer at a temperature of from about 235° C. to about 265° C. to form a solid state polymerized PEN product.

This is a division, of application Ser. No. 08/357,619, filed Dec. 15,1994, now abandoned.

FIELD OF THE INVENTION

This invention relates to a process for solid state polymerizingpoly(ethylene naphthalate), specifically applicable to a foamedpoly(ethylene naphthalate) prepolymer.

BACKGROUND OF THE INVENTION

High molecular weight polyesters are commonly produced from lowmolecular weight polyesters of the same composition by solid statepolymerization. The low molecular weight polyesters which are used insuch solid state polymerizations are generally prepared by conventionalmelt polymerization. The molten polyester product of such meltpolymerizations is converted to solid granules in the shape of pellets,chips, or cubes. Solid state polymerization of such pellets, chips, orcubes is generally considered advantageous in that the handling of highmolecular weight ultra-high viscosity molten polymers is eliminated.Thermal degradation is also essentially avoided during the solid stateportion of the polymerization.

Solid state polymerization of a polyester involves two major steps:chemical reaction and diffusion of reaction byproducts, e.g. water andethylene glycol. Therefore, the solid state polymerization rate can beincreased by reducing the diffusional resistance within the prepolymergranules. The diffusional resistance can be reduced by reducing theprepolymer particle size. However, smaller granules have highertendencies to stick together during solid state polymerization, causingprocess difficulties. Therefore, there exists a minimum particle sizethat is suitable for solid state polymerization.

Several methods have been proposed to reduce diffusional resistancewhile maintaining a suitable particle size. U.S. Pat. No. 3,586,647(Kremer) proposes foamed pellets which are formed by dispersing nitrogenor a foaming agent into the prepolymer melt before pelletizing. We havefound that the improvement in the solid state polymerization rate ofpoly(ethylene terephthalate) (PET) by using foamed pellets is onlybetween 20 and 35%. Because the cells within the foamed pellets areclosed, the improvement in the solid state polymerization rate throughuse of foamed pellets will be somewhat limited. U.S. Pat. No. 4,755,587(Rinehart) proposes porous pellets with interconnected voids. Porous PETpellets solid state polymerize 2 to 3 times as fast as standard solidPET pellets. Since the voids inside each porous pellet areinterconnected, a great improvement in the solid state polymerizationrate can be achieved by using porous pellets. Although porous pelletsoffer greatly improved solid state polymerization rates, the formationof porous pellets involves expensive operations-grinding, compacting,and classifying, etc.--and porous pellets tend to generate large amountsof fines, which impacts productivity.

Because of its high strength and barrier properties, poly(ethylenenaphthalate) (PEN) is an excellent material for the applications ofbeverage and food containers and industrial fibers. Due to its extremelyhigh melt viscosity, PEN with an intrinsic viscosity suitable for suchapplications cannot be produced by melt state polymerization processalone. Instead, it must be produced by a combination of melt state andsolid state polymerization processes. Because of the high barrierproperties of PEN, the solid state polymerization rate is relativelyslow. It is also known that PEN is preferably devolatilized prior tosolid state polymerization, as described in U.S. Pat. No. 4,963,644(Duh).

We have discovered that the solid state polymerization rate of PEN canbe dramatically improved by using foamed PEN prepolymer granules. Themagnitude of this rate improvement is surprisingly unexpected, even inview of the known improvement that results when foamed PET is solidstate polymerized. In our investigation of the solid statepolymerization rate of foamed PEN granules, we found that the solidstate polymerization rate improvement by foamed PEN granules overstandard solid PEN granules was surprisingly high-exceeding even thesolid state polymerization rate improvement by porous PET granules overthe standard solid PET granules, if the foamed PEN granules aredevolatilized prior to crystallization and solid state polymerization.The use of a foamed PEN prepolymer, combined with a devolatilizationstep prior to solid state polymerization, provides a particularly fastand productive solid state polymerization process for a PEN polymer.

SUMMARY OF THE INVENTION

This invention includes a process for preparing a solid statepolymerized PEN polymer comprising: (1) preparing a molten PEN polymerwith an intrinsic viscosity of from about 0.25 dl/g to about 0.55 dl/g,(2) dispersing an inert gas into the molten PEN polymer to form a foamedPEN polymer with a void fraction of from about 0.10 to about 0.50, (3)forming the foamed PEN polymer into granules, (4) devolatilizing thegranular PEN polymer at a temperature of from about 80° C. to about 140°C., (5) crystallizing the devolatilized PEN polymer at a temperature offrom about 150° C. to about 260° C., and (6) solid state polymerizingthe crystallized PEN polymer at a temperature of from about 235° C. toabout 265° C. to form a solid state polymerized PEN product. The subjectinvention also includes the product of this process, and a method forobtaining a PEN polymer with a reduced melting point.

DETAILED DESCRIPTION OF THE INVENTION

The PEN prepolymer utilized in accordance with the present invention istypically prepared by standard melt polymerization techniques. Such meltpolymerizations result in the formation of PEN which is essentiallyamorphous in nature. By this we mean that the PEN is virtually totallyamorphous even though it may contain small regions where crystallinityexists. The PEN homopolymer is generally produced by melt polymerizingethylene glycol with an alkyl diester of a naphthalene dicarboxylicacid, such as dimethyl-2,6-naphthalene dicarboxylate. Alternatively, thePEN is produced by polymerizing ethylene glycol with a naphthalenedicarboxylic acid monomer, such as 2,6-naphthalene dicarboxylic acid.

The PEN utilized in this invention can be a modified PEN. A modifiedPEN, or PEN copolymer, contains small amounts of repeat units which arederived from acids other than naphthalene dicarboxylic acid and/orglycols other than ethylene glycol. For instance, small amounts ofisophthalic acid or terephthalic acid can be used in the diacidcomponent utilized in preparing the PEN. PEN which has been modifiedwith a small amount of a diol containing from 3 to 8 carbon atoms isalso representative of a modified PEN which can be used. For instance, asmall amount of 1 A-butane diol can be utilized in the glycol componentused in preparing the modified PEN. Normally, no more than about 20 molepercent of the repeat units in such modified PEN will be derived fromdiacids or diols other than naphthalene dicarboxylic acid and ethyleneglycol. It is, of course, contemplated that diesters of suchdicarboxylic acids and diols can be used. In most cases, such modifiedPEN will contain not more than about 15 mole percent units derived fromdiacids other than naphthalene dicarboxylic acid and/or less than 5 molepercent units derived from diols other than ethylene glycol. It willnormally be preferred for such modified polyesters to contain not morethan about 10 mole percent units derived from dicarboxylic acids otherthan naphthalene dicarboxylic acid and/or less than 5 mole percent unitsderived from glycols other than ethylene glycol.

In the process of the invention, an inert gas is dispersed into the PENprepolymer while it is in a molten state, and prior to granulation.Nitrogen is suitable for the inert gas, but other gases which would beinert to the polymer under melt polymerization conditions may also beemployed. Injection of the gas at high pressure is not required, butmust be sufficient to adequately disperse the gas into the moltenpolymer. Higher pressures require smaller injection volumes to provide agiven void fraction, but also require better mixing to ensure uniformdispersion of the gas within the molten polymer. The formation of solidpolymer with an excessive void fraction should be avoided. Such polymerwould have insufficient density to provide cost-effective polymerproduction rates. Also, since the solid polymer typically passes throughat least some process equipment by gravity flow, polymer with anexcessive void space may be too lightweight to provide sufficientgravity flow rates, resulting in bridging and plugging in the processequipment. The foamed granules formed from the molten polymer will havea void fraction of from about 0.10 to about 0.50, preferably from about0.15 to about 0.30, and most preferably from about 0.20 to about 0.25,to provide the advantage of enhanced solid state polymerization rateswhile avoiding the disadvantages associated with excessive voidfraction.

To ensure uniform dispersion of the inert gas within the PEN prepolymer,it is necessary to keep the intrinsic viscosity (IV) of the PEN polymerless than about 0.60 dl/g. A PEN polymer that has reached an IV of fromabout 0.25 dl/g to about 0.55 dl/g will allow good dispersion of theinert gas, and have sufficient melt strength that it can be converted togranular form (e.g. pellets, cubes, etc.) for solid statepolymerization. The IV of the PEN polymer is measured in a 60:40phenol:tetrachloroethane mixed solvent system at a temperature of 30° C.Given the very high melt viscosity of PEN polymer, and the high solidstate polymerization rates possible with foamed PEN prepolymer, it maybe economically advantageous to set the prepolymer product IV at theminimum level acceptable for pelletizing or dicing. This will facilitatefoaming the prepolymer, and allow the polymer IV to be efficientlyincreased in the solid state to a level desired for the solid statedproduct.

The low molecular weight PEN prepolymers which are subsequentlypolymerized in the solid state, are generally convened to a solid formthrough rapid cooling and pelletizing, dicing, etc. the polymer intopellets, chips, or cubes. Such granules can vary greatly in size;however, as a general rule, the smaller the size of the granules, thefaster any reaction byproducts will be driven off in the subsequentsolid state polymerization.

In the devolatilization step, the amorphous PEN prepolymer is heated toa temperature within the range of about 80° C. to about 140° C. in thepresence of a purge gas or under a vacuum to devolatize the amorphousPEN. This devolatilization procedure is preferably conducted at atemperature which is within the range of about 115° C. to about 137° C.It is more preferred for the devolatilization to be done at atemperature of from about 120° C. to about 135° C. The devolatilizationstep can be carried out as either a batch or a continuous operation.

The purge gas utilized in the devolatilization procedure can be any gaswhich does not react with the PEN prepolymer under devolatilizationconditions. Since the PEN prepolymer is relatively stable at thedevolatilization temperature, air can be used as the purge gas. It is,of course, also possible to utilize nitrogen, or a noble gas such ashelium or neon in the devolatilization procedure. Even though it ispossible to carry out the devolatilization step under a vacuum, it isnormally preferred to carry out the devolatilization in the presence ofa stream of a purge gas because the purge gas can be preheated to thedevolatilization temperature to provide improved heat transfer.

The devolatilization step is carried out for a period of time which issufficient to remove most of the volatile materials, such as water,ethylene glycol, and acetaldehyde from the PEN prepelymer. It is, ofcourse, desirable to remove virtually all of the volatile compounds fromthe PEN prepolymer prior to crystallization. The amount of time requiredfor the devolatilization step will depend upon the temperaturesutilized. Higher temperatures naturally require shorter periods of timeto achieve a requisite degree of devolatilization. For example, at atemperature of 115° C. the time required for devolatilization is aboutfour hours. At a temperature of 130° C. only about two hours is requiredfor devolatilization. The optimum period of time required fordevolatilization will also be somewhat dependent upon the equipmentutilized and upon the size and shape of the granules. The time requiredfor devolatilization in a continuous process will typically be withinthe range of 15 minutes to 10 hours and will more typically be withinthe range of 30 minutes to 4 hours.

Since the devolatilization procedure is carried out at a temperaturebelow the sticking temperature of the amorphous PEN prepolymer,agitation is not required during the devolatilization step. Accordingly,a hopper type devolatilizer can be utilized wherein the amorphous PENprepolymer granules are continuously charged into the top of the hopperand are allowed to move through the hopper by gravity countercurrent tothe flow of purge gas. The devolatilized granules leaving the bottom ofthe hopper devolatilizer can then be continuously fed into acrystallizer. Alternatively, devolatilization can be conducted in ahorizonal vessel, with agitation to move the polymer through the vessel.In a batch operation, a tumbling vessel may be used.

Use of this devolatilization step is particularly critical when foamedPEN polymers are to be solid state polymerized. It is known that solidPEN granules will greatly expand and stick together to form aninseparable mass when directly exposed to crystallization temperatures.This phenomenon has been determined to be the result of rapid release ofbyproducts inside the granules at temperatures approaching the softeningpoint of the PEN polymer and prior to significant crystallization of thepolymer. By devolatilizing the solid PEN granules prior tocrystallization, volatile materials trapped inside the granules aregradually removed, and agglomeration is avoided. Foamed PEN granulesexpand and agglomerate even more severely than solid PEN granules whenexposed directly to crystallization temperatures. Since the foamedgranules have a lower weight for a given size of granule, and thereforea lower density, the severe distortion of the foamed granules may be dueto the greater expansion that occurs relative to a given weight of PEN.Use of a devolatilization step prior to crystallization and solid statepolymerization of foamed PEN granules also appears to enhance the solidstate polymerization rate for the foamed PEN granules. This may be dueto fractures occurring within the granules, connecting some of the voidspaces within the granules, due to expansion of the inert gas presentwithin the foamed PEN, and to the rapid expansion of reactionbyproducts, during the devolatilization

In the crystallization step, the devolatilized PEN prepolymer is heatedto a temperature within the range of about 150° C. to about 260° C. tocrystallize the polymer. When an amorphous polyester is heatedsignificantly above its glass transition temperature (T_(g)), it willbecome sticky before it starts to crystallize. PEN has a T_(g) of about118° C., and it exhibits a crystallization peak between 180° C. and 220°C., and its sticking temperature is about 140° C. when in the amorphousstate. Therefore, according to conventional wisdom, the preferredcrystallization temperature range for PEN would be between 180° C. and220° C. It is typically more preferred for the crystallizationtemperature to be within the range of 190° C. to 205° C.

It is important for the crystallization step to be conducted while thePEN prepolymer is being agitated to prevent sticking. The requisitedegree of agitation can be provided by utilizing a crystallizer whichhas a fluidized or vibrating bed. In such fluidized bed crystallizers, apurge gas is typically allowed to flow through the crystallizer at arate sufficient to maintain the prepolymer cubes or pellets in thefluidized state. It is, of course, also possible to perform thecrystallization step in an agitated vessel which provides sufficientagitation so as to prevent sticking or agglomeration of the PENprepolymer pellets or cubes.

The amount of time required for the crystallization step will dependupon the temperatures utilized. Higher temperatures naturally requireshorter periods of time to achieve a requisite degree ofcrystallization. The optimum period of time required for crystallizationwill also be somewhat dependent upon the equipment utilized and the sizeand shape of the polymer granules. Because polyester granules enteringthe crystallizer in a continuous process have been preheated to near thesticking temperature, they can be heated in the crystallizer to thecrystallization temperature and crystallized quickly. This leads to ashorter polymer sticky stage and more uniform granule temperature andcrystallinity, and hence a more stable and efficient process. The timerequired for crystallization will typically be within the range of about1 minute to about 4 hours. In a continuous process, the crystallizationstep will normally take about 2 minutes to about 30 minutes. Thecrystallization step can be carried out as either a batch or acontinuous operation.

After the PEN prepolymer has been crystallized, it can be solid statepolymerized in a batch or continuous process. Suitable solid statepolymerization temperatures can range from a temperature just above thethreshold temperature of the polymerization reaction up to a temperaturewithin a few degrees of the sticking temperature of the PEN prepolymerwhich can be well below its melting point. The solid statepolymerization temperature utilized will typically be from about 1° C.to about 50° C. below the sticking temperature of the crystallized PENprepolymer. The optimum solid state reaction temperature will differsomewhat for polymers of different molecular weights, and compositions(e.g. PEN homopolymers and PEN copolymers).

As a general rule, the optimum solid state polymerization temperaturefor the PEN prepolymer will be from about 5° C. to about 20° C. belowits sticking temperature. For example, in the solid state polymerizationof crystalline PEN, the temperature employed normally ranges from about210° C. to about 265° C. Generally, the crystalline PEN prepolymer willbe solid state polymerized at a temperature of from about 230° C. toabout 265° C. In most cases, PEN prepolymer will be solid statepolymerized at a temperature of from 240° C. to 260° C.

The solid state polymerization is conducted under a vacuum or, moretypically, in the presence of a stream of an inert gas. It is highlydesirable for the inert gas to flow uniformly throughout the solid statepolymerization zone which is filled with the polyester prepolymer whichis being polymerized. A good polymerization reactor will be designed insuch a way that the inert gas will flow evenly through the polyesterprepolymer in it. It should be noted that the inert gas actually flowsaround the polyester prepolymer granules as it streams through the solidstate polymerization zone. Some suitable inert gases for use in thesolid state polymerization process of this invention include nitrogen,carbon dioxide, helium, argon, neon, krypton, zeon, and certainindustrial waste gases. Various combinations or mixtures of differentinert gases can also be used. In most cases nitrogen will be used as theinert gas.

The PEN prepolymer is solid state polymerized for a time sufficient toincrease its molecular weight or IV to that of the high molecular weightPEN resin desired. It is desirable for the high molecular weight PENresin being prepared to have an IV of at least 0.5 dl/g. In most casesthe high molecular weight resin will have an IV of at least about 0.65dl/g and for some applications will preferably have an IV of at leastabout 0.75 dl/g. The polymerization time needed will normally range fromabout 1 to about 24 hours and in most cases will range from 4 to 14hours.

Use of foamed PEN prepolymer allows use of a lower solid statepolymerization temperature to achieve the same target IV for the solidstated product, with the same solid state polymerization time. While themelting point temperature (T_(m)) of PET is affected only slightly bythe solid state polymerization temperature used, we have found that themelting point temperature (T_(m)) for solid stated PEN polymer ingeneral increases about 5° C. to 10° C. with every 10° C. increase insolid state polymerization temperature. With foamed PEN prepolymer, itis therefore possible to produce high molecular weight solid stated PENresins (e.g. IV of 0.70 dl/g) with lower melting points (e.g. less than270° C.), by using lower solid state polymerization temperatures (e.g.240° C.) with reasonable solid state polymerization times (e.g. lessthan 6 hours). Use of lower temperatures for solid state polymerizationmay also allow use of equipment designed to solid state polymerize PETpolymer, which is typically solid state polymerized at less than 230°C., to solid state polymerize PEN polymer.

Production of a solid state polymerized PEN polymer with a lower T_(m)also provides a benefit during subsequent processing of the polymer intoarticles such as bottles. We have found that the acetaldehyde generationrate doubles for every 15° C. increase in polymer processing temperaturefor PEN. Consequently, a PEN polymer with a lower may be processed at alower processing temperature into articles such as bottles that containa lower acetaldehyde content. Polymers with lower T_(m) are alsogenerally easier to process into finished articles. Low acetaldehydecontent is particularly important for some finished articles, such asmineral water bottles.

The unexpectedly great effect of foaming of prepolymer granules on thesolid state polymerization rate for PEN polymer may be attributed toseveral factors. Because of the higher barrier property of PEN polymer,a greater reduction in the diffusional resistance can be achieved byfoaming. Amorphous PEN polymer is quite brittle, consequently, dicing orpelletizing tends to crack open the cells within the foamed cubes orpellets. In addition, the relatively large amounts of byproducts trappedinside the foamed PEN cubes may open up the cells as they escape fromwithin the granules during devolatilization.

This invention is illustrated by the following examples which are merelyfor the purpose of illustration and are not to be regarded as limitingthe scope of the invention or the manner in which it can be practiced.

Example 1

Foamed and unfoamed PEN prepolymers with a target IV of 0.50 dl/g in theform of 1/8 inch cubes were prepared and solid state polymerized atthree temperatures (240° C., 250° C. and 260° C.) to compare their solidstate polymerization rates.

The last stage of the melt state polymerization used to prepare theprepolymer is normally conducted under vacuum. When the desiredprepolymer IV is reached, the reactor is pressurized to about 45 psigwith nitrogen, and the molten prepolymer is extruded and pressed into a1/8 inch ribbon. The ribbon is solidified by quenching with cold water,and then diced into 1/8 inch cubes. In the normal production of standardsolid prepolymer cubes, the agitation is stopped before the reactor ispressurized. To produce foamed cubes for this example, the agitation waskept running during pressurizing to whip nitrogen into the prepolymermelt. Depending on the speed and duration of the agitation after thecompletion of the melt state polymerization and the final reactorpressure used, foamed cubes with various porosities can be obtained. Onebatch each of solid and foamed PEN prepolymer cubes were produced forthis example. The IV's of the solid and foamed PEN prepolymers were0.500 dl/g and 0.497 dl/g respectively. The bulk density of the foamedPEN cubes was 79.4% of that of the solid PEN cubes. Therefore, the voidfraction of the foamed PEN cubes was about 0.21.

A glass, tube-shaped reactor, 1 inch in diameter and 20 inches inlength, was used to conduct the solid state polymerization experiments.During the solid state polymerization experiments, the reactor wasimmersed in a thermostatted oil bath, and a stream of nitrogen,preheated to the reactor temperature, was passed through the bottom ofthe reactor to sweep away the reaction byproducts. In each solid statepolymerization run, 80 grams of PEN prepolymer cubes were charged to thereactor.

In the standard procedure for solid state polymerization of PET, the PETprepolymer granules are directly exposed to the crystallizationtemperature (160° C. to 200° C.) to effect crystallization. However,when either foamed or solid PEN prepolymer cubes were directly exposedto the crystallization temperature (170° C. to 220° C.), the cubesexpanded greatly and stuck together to form lumps, which were verydifficult to separate, as the polymer temperature reached the softeningpoint before significant crystallization took place. This phenomenon hasbeen determined to be due to the sudden volatilization of byproducts(water, ethylene glycol, and acetaldehyde, etc.) trapped inside the PENcubes near the softening point. In the case of foamed cubes, thenitrogen or other inert gas remaining in the voids within the cubes alsocontributes to the sudden expansion and worsens the sticking problem. Tocircumvent this problem, the PEN prepolymer was devolatilized at 125°C., which is below the softening point of amorphous PEN, in a stream ofnitrogen for 2 hours before the crystallization step, to slowly removemost of the trapped byproducts. Then the prepolymer was crystallized andfurther dried at 200° C. for 60 minutes. With this devolatilizationstep, no sudden expansion and sticking were encountered. The reactortemperature was then raised to the desired reaction temperature (240°C., 250° C., or 260° C.) to effect the solid state polymerization whichlasted for 23 to 24 hours. Solid state polymerization runs, each with adifferent reaction temperature (240° C., 250° C., or 260° C.) wereconducted for each of the foamed and, for comparison, unfoamed PENprepolymers. The IV's of the foamed and unfoamed PEN samples taken atvarious periods of solid state polymerization time during the six solidstate polymerization runs are listed in Table 1.

For comparison, the solid PEN prepolymer was also used to prepare porouspellets for a solid state polymerization test. Samples of solid PENcubes were ground in a Wiley mill through a 60 mesh screen. The powderobtained was screened with a 100 mesh sieve. The fraction retained onthe 100 mesh sieve was used to prepare porous pellets with a Parr PelletPress using a 1/8 inch die and 1200 pounds per square inch (psi)pressure. The resulting porous pellets were 1/8 inch in diameter and3/16 inch in length. The bulk density of the PEN porous pellets was 85%of that of the PEN solid cubes. Because of the high rigidity and lowtackiness of amorphous PEN, the durability of the porous pellets waspoor. The PEN porous pellets thus obtained were solid state polymerizedusing the same procedure given above. Only one solid statepolymerization run with a reaction temperature of 250° C. was conductedfor the porous pellets. Because the porous pellets solid statepolymerized very rapidly, the reaction was terminated after 7.5 hours.At the end of the solid state polymerization, PEN fines, weighing about17% of the total weight of the PEN porous pellets charged, wererecovered from the bottom of the reactor tube. These fines arose as aresult of partial disintegration of the porous pellets during theexperimental run. This could be a serious problem considering thatdisturbance of the porous pellet bed during the experimental run waskept to a minimum. In a commercial solid state polymerization process,which requires vigorous agitation at least during the crystallizationstep, a major fraction of the mass of the PEN porous pellets will falloff to generate a large amount of fines. The PEN porous pellet samplestaken during the solid state polymerization run were also tested for IV.The results are included in Table 1. Because of the IV data for thesolid state polymerization of PEN porous pellets appeared to scattermore than for PEN solid and foamed cubes, duplicate IV tests wereperformed for each solid stated PEN porous pellet samples.

For comparison, foamed and unfoamed PET prepolymer cubes with a targetIV of 0.58 dl/g were produced by methods similar to those used for thePEN prepolymers. The bulk density of the foamed PET cubes was 88% ofthat of the unfoamed PET cubes. Therefore the void fraction of thefoamed PET cubes was estimated to be 0.12. Samples of these PETprepolymers were also solid state polymerized using a standard procedurenormally used for PET. No devolatilization step was required for the PETprepolymers. The PET prepolymer was first crystallized and dried at 180°C. for 60 minutes, and then the reactor temperature was raised to 220°C. to effect the solid state polymerization, which lasted for 24 hours.Only one solid state polymerization was conducted for each PETprepolymer. Samples taken at different periods of solid statepolymerization time were tested for IV. Table 2 lists the IV's of thefoamed and unfoamed PET samples taken during the solid statepolymerization runs.

The IV data in Tables 1 and 2 can be used to prepare polymer IV vs solidstate polymerization (SSP) time plots for all the SSP runs conducted forthe PEN and PET prepolymers. From these plots, the SSP times requiredfor the PEN prepolymers to achieve 0.70 and 0.80 dl/g IV's at 240° C.,250° C., and 260° C. and the SSP times required for the PET prepolymersto achieve 0.80 dl/g and 0.95 dl/g IV's at 220° C. can be determined.The SSP time requirements thus determined are listed in Table 3.

From these SSP time requirement data, the SSP rate advantages of foamedPEN over unfoamed PEN and foamed PET over unfoamed PET can be calculatedfor each product IV at each SSP temperature. For example, the SSP timesrequired for the foamed and unfoamed PEN to achieve a product IV of 0.80dl/g were 5.1 hours and 23.0 hours respectively at 250° C. Thus thefoamed PEN solid state polymerized 4.51 times as fast as unfoamed PENand the SSP rate advantage of foamed PEN was 351% over unfoamed PEN. TheSSP rate advantage data thus determined are also included in Table 3 forthe foamed and unfoamed PET. Since the productivity of a solid statepolymerization reactor is measured in terms of polymer weight per hours,it is necessary to factor in the lower bulk densities of the foamed PENand PET (compared with the unfoamed PEN and PET respectively) todetermine the SSP productivity advantages. The SSP productivityadvantages of foamed PEN over unfoamed PEN and foamed PET over unfoamedPET thus obtained are also included in Table 3. Similarly, the rate andproductivity advantages of PEN porous pellets over foamed and unfoamedPEN were determined and their values are also included in Table

It can be seen in Table 3 that the foamed PEN solid state polymerizedfrom about 4 times (in the IV range of 0.50-0.70 dl/g at 240° C.) toabout 4.5 times (in the IV range of 0.50-0.80 dl/g at 250° C.) as fastas the unfoamed PEN. Adjusted for its lower bulk density, foamed PENoffered productivity advantages of at least 200% over unfoamed PEN.These exceptionally high SSP rate and productivity advantages of foamedPEN prepelymer were unexpected based on the modest SSP rate andproductivity advantages of foamed PET prepolymer over unfoamed PETprepolymer.

In comparison, it can be seen in Table 3 that the foamed PET had SSPrate advantages of only 20.3% and 32.0% for products of IV's of 0.80dl/g(for bottle application) and 0.95 dl/g (for frozen food trayapplication) respectively. Adjusted for its lower bulk density, thefoamed PET had SSP productivity advantages of 5.9% and 16.2%respectively over the unfoamed PET. While these advantages aresignificant, they are quite low compared with that of foamed PEN overunfoamed PEN.

These observations may be explained by the following two reasons: First,PEN has a much higher barrier property than PET and the SSP of PEN ismore diffusionally controlled than the SSP of PET. Therefore, anymeasure that contributes to a reduction in diffusional resistance (e.g.foaming) will result in a greater increase in the SSP rate. Secondly,during the devolatilization step, the release of the relatively largeamounts of byproducts as well as nitrogen trapped inside the foamed PENgranules opened up the cells or voids, thereby greatly enhancing thediffusion rates of the reaction byproducts and the overall SSP rateduring solid state polymerization. Although porous PEN pellets alsooffered a significant SSP rate advantage, it is impractical to producehigh IV PEN via porous pellets because of pellet durability problems.

Besides significant improvements in SSP rate and productivity, the useof foamed PEN prepolymer instead of standard unfoamed PEN prepolymeroffers another advantage; namely, it facilitates economical productionof solid stated PEN resins with substantially lower melting points. Lowmelting PEN resin is particularly suitable for applications, such assoft drink bottles and food containers, where low acetaldehyde contentis important.

The melting point of solid stated PEN is primarily a function of SSPtime and temperature-molecular weight or IV has very little effect onthe melting point. The effects of SSP time and temperature on themelting point of PEN are much greater than on PET and are of particularinterest here. At a fixed SSP temperature, the melting point of PEN atfirst decreases with the SSP time and reaches a minimum, and thenincreases monotonously as the SSP is continued until it reaches anequilibrium value. Thus, at an SSP temperature of 240° C., the meltingpoint of PEN decreases from about 268° C. to a minimum value of about264.5° C. in about 6 hours, and then increases monotonously as the SSPis continued. At an SSP temperature of 250° C. or higher, the meltingpoint reaches the minimum within 30 minutes and the minimum value isonly slightly lower than the initial value. In general, the meltingpoint of PEN after a fixed SSP time increases by 5° C. to 10° C. foreach 10° C. increase in the SSP temperature. Therefore, based on the SSPtime required and the SSP

temperature used, the melting point of each of the solid stated PET andPEN products listed in Table 3, regardless of its form, can be estimatedwith reasonable accuracy. The estimated melting point of each solidstated product is also included in Table 3.

Example 2

The following is an example that demonstrates how a solid stated PENproduct with a substantially lower melting point can be produced with areasonably short SSP time by using foamed prepolymer instead of unfoamedprepolymer.

The maximum safe temperature for a continuous solid state polymerizationof PEN in a moving-bed reactor is about 250° C. To produce 0.70 dl/g IVsolid PEN cubes for bottle application at a reactor temperature of 250°C., a residence time of 12.3 hours is required. This solid stated PENbottle resin will have a melting point of 277.8° C. (see Table Althoughit may be feasible to produce 0.70 dl/g IV solid PEN with asignificantly lower melting point (271.0° C.) by using a lower reactortemperature of 240° C., the much longer residence time required (22.0hours) will make the process less economical. If foamed PEN prepolymeris used in place of the standard unfoamed PEN prepolymer, 0.70 dl/g IVsolid stated product with a melting point of 264.5° C. can be producedwith a relatively short residence time of 5.6 hours at a reactortemperature of 240° C. Not only is the product melting point about 13°C. lower, but also the solid stating residence time is about 47% shorterthan for the standard process using unfoamed prepolymer and a reactortemperature of 250° C.

Solid stated PEN with a lower melting point not only is easier toprocess, but also allows use of a lower melt processing temperatureyielding end products with a lower acetaldehyde content. We havedetermined that the acetaldehyde generation rate of PEN in itsmelting-processing temperature range approximately doubles for each 15°C. increase in temperature. We have further determined that over 95% ofthe acetaldehyde content of the PEN bottle preforms is contributed bythe acetaldehyde generated during the injection molding step. It will bereasonable to assume that foamed PEN bottle resin with a melting pointof 13° C. lower than the standard solid PEN bottle resin can beinjection molded at a barrel temperature of about 13° C. lower than thestandard barrel temperature, yielding preforms with at least 40% loweracetaldehyde content. Consequently, foamed PEN polymer can providefinished articles with significantly lower acetaldehyde content. Becauseof this property advantage, and the enhanced SSP rates possible, webelieve that among the three forms of PEN prepolymers, foamed granulateis the preferred form for use in solid state polymerization.

                  TABLE 1                                                         ______________________________________                                        Intrinsic Viscosity of Foamed and Solid                                       PEN and Porous PEN Samples Taken at Various Times During                      Solid State Polymerization (SSP) at Various Temperatures                                           Intrinsic Viscosity (dl/g)                                         Reaction Time                                                                            Reaction Temperature                                     Prepolymer Form                                                                           (hours)      240° C.                                                                        250° C.                                                                      260° C.                         ______________________________________                                        Foamed Cubes                                                                              0            0.500   0.500 0.500                                              1.0          0.551   0.579 0.637                                              2.5          0.610   0.675 0.767                                              4.5          0.667   0.775 0.911                                              7.5          0.738   0.890 1.069                                              11.0         0.811   0.990 1.175                                              15.0         0.862   1.071 1.249                                              19.0         0.923   1.126 1.287                                              24.0         0.978   1.172 1.353                                  Solid Cubes 0            0.497   0.497 0.497                                              1.0          0.514   0.525 0.558                                              2.75         0.539   0.554 0.612                                              4.5          0.566   0.601 0.664                                              7.5          0.591   0.640 0.727                                              12.0         0.640   0.700 0.784                                              17.0         0.665   0.724 0.864                                              23.0         0.714   0.789 0.896                                  Porous Pellets                                                                            0                    0.497                                                    1.0                  0.779                                                    1.0                  0.797                                                    2.5                  0.921                                                    2.5                  0.934                                                    4.75                 1.014                                                    4.75                 1.045                                                    7.5                  1.258                                                    7.5                  1.188                                        ______________________________________                                    

                  TABLE 2                                                         ______________________________________                                        Intrinsic Viscosities of Solid and Foamed PET Samples Taken                   During Solid State Polymerization at 220° C.                           Reaction Time  Intrinsic Viscosity (dl/g)                                     (hours)        Foamed PET Solid PET                                           ______________________________________                                        0              0.579      0.580                                               1              0.630      0.617                                               2.5            0.667      0.670                                               4              0.727      0.717                                               6              0.789      0.762                                               9              0.864      0.826                                               12             0.934      0.880                                               18             1.040      0.963                                               21             1.087      0.999                                               24             1.134      1.031                                               ______________________________________                                    

                                      TABLE 3                                     __________________________________________________________________________    Comparison of Solid State Polymerization of PEN and PET in Various            Prepolymer Forms                                                              Prepolymer                                                                           SSP Temperature        220° C.                                                                        240° C.                                                                       250° C.                                                                          260° C.         Form   Product IV (dl/g)      0.80                                                                              0.95                                                                              0.70                                                                              0.80                                                                             0.70 0.80 0.70                                                                              0.80               __________________________________________________________________________    PEN    SSP Time Required (hrs.)       5.6  10.5                                                                            3.0  5.1  1.6 2.8                Foamed Product T.sub.m (°C.)   264.5                                                                             267.5                                                                            269.5                                                                              272.0                                                                              273.5                                                                             275.5              Cubes  SSP Rate Advantage over Solid PEN (%)                                                                        293 -- 310  351  294 329                       Productivity Advantage over Solid PEN (%)                                                                    212 -- 214  258  213 249                PEN    SSP Time Required (hrs.)       22.0   12.3 23.0 6.3 12.3               Solid Cubes                                                                          Product T.sub.m (°C.)   271.0  277.8                                                                              281.0                                                                              279.5                                                                             283.3              PET    SSP Time Required (hrs.)                                                                             7.7 16.9                                        Solid Cubes                                                                          Product T.sub.m (°C.)                                                                         252.3                                                                             246.5                                       PET    SSP Time Required (hrs.)                                                                             6.4 12.8                                        Foamed Product T.sub.m (°C.)                                                                         252.4                                                                             245.0                                       Cubes  SSP Rate Advantage over Solid PET (%)                                                                20.3                                                                              32.0                                               Productivity Advantage over Solid PET (%)                                                            5.9 16.2                                        PEN    SSP Time Required (hrs.)              0.65 1.3                         Porous Product T.sub.m (°C.)          268.0                                                                              268.5                       Pellets                                                                              SSP Rate Advantage over Solid PEN (%) 1790 1670                               SSP Rate Advantage over Foamed PEN (%)                                                                              362  292                                Productivity Advantage over Solid PEN (%)                                                                           1510 1405                               Productivity Advantage over Foamed PEN (%)                                                                          394  320                         __________________________________________________________________________

I claim:
 1. A high molecular weight solid state polymerized,poly(ethylene naphthalate) polymer product, prepared by a processcomprising:preparing a molten poly(ethylene naphthalate) polymer with anintrinsic viscosity of from about 0.25 dl/g to about 0.55 dl/g;dispersing an inert gas into the molten poly(ethylene naphthalate)polymer to form a foamed poly(ethylene naphthalate) polymer with a voidfraction of from about 0.10 to about 0.50; forming the foamedpoly(ethylene naphthalate) polymer into granules suitable for solidstate polymerization; devolatilizing the granular poly(ethylenenaphthalate) polymer at a temperature of from about 80° C. to about 140°C.; crystallizing the devolatilized poly(ethylene naphthalate) polymerat a temperature of from about 150° C. to about 260° C.; solid statepolymerizing the crystallized poly(ethylene naphthalate) polymer at atemperature of from about 210° C. to about 265° C. to form a solid statepolymerized poly(ethylene naphthalate) polymer product.
 2. The productof claim 1 wherein the molten poly(ethylene naphthalate) polymer has anintrinsic viscosity of from about 0.25 dl/g to about 0.45 dl/g.
 3. Theproduct of claim 2 wherein the inert gas is nitrogen.
 4. The product ofclaim 3 wherein the foamed poly(ethylene naphthalate) polymer has a voidfraction of from about 0.15 to about 0.30.
 5. The product of claim 3wherein the foamed poly(ethylene naphthalate) polymer has a voidfraction of from about 0.20 to about 0.25.
 6. The product of claim 3wherein the foamed poly(ethylene naphthalate) polymer is formed intofoamed cubes for solid state polymerization.
 7. The product of claim 3wherein the foamed poly(ethylene naphthalate) polymer is formed intofoamed pellets for solid state polymerization.
 8. The product of claim 3wherein the poly(ethylene naphthalate) polymer is devolatilized at atemperature of from about 120° C. to about 130° C.
 9. The product ofclaim 3 wherein the poly(ethylene naphthalate) polymer is crystallizedat a temperature of from about 190° C. to about 205° C.
 10. The productof claim 3 wherein the poly(ethylene naphthalate) polymer is solid statepolymerized at a temperature of from about 230° C. to about 265° C. 11.The product of claim 1 wherein the poly(ethylene naphthalate) is apoly(ethylene naphthalate) homopolymer.
 12. The product of claim 1wherein the poly(ethylene naphthalate) is a poly(ethylene naphthalate)copolymer.
 13. The product of claim 12 wherein the poly(ethylenenaphthalate) contains no more than about 20 mole percent repeat unitsderived from terephthalic acid.
 14. The product of claim 9 wherein thepoly(ethylene naphthalate) polymer is solid state polymerized at atemperature of 240° C. or more, and the solid state polymerizedpoly(ethylene naphthalate) polymer has a product IV of at least 0.70dl/g and a melting point of less than 270° C.
 15. The product of claim 9wherein the poly(ethylene naphthalate) polymer is solid statepolymerized at a temperature of 250° C. or more, and the solid statepolymerized poly(ethylene naphthalate) polymer has a product IV of atleast 0.70 dl/g and a melting point of less than 275° C.
 16. The productof claim 9 wherein the poly(ethylene naphthalate) polymer is solid statepolymerized at a temperature of 260° C. or more, and the solid statepolymerized poly(ethylene naphthalate) polymer has a product IV of atleast 0.70 dl/g and a melting point of less than 278° C.
 17. A highmolecular weight solid state polymerized poly(ethylene naphthalate)polymer product, prepared by a process comprising:preparing a moltenpoly(ethylene naphthalate) polymer with an intrinsic viscosity of fromabout 0.25 dl/g to about 0.55 dl/g; dispersing nitrogen into the moltenpoly(ethylene naphthalate) polymer to form a foamed poly(ethylenenaphthalate) polymer with a void fraction of from about 0.15 to about0.30; forming the foamed poly(ethylene naphthalate) polymer intogranules suitable for solid state polymerization; devolatilizing thegranular poly(ethylene naphthalate) polymer at a temperature of fromabout 120° C. to about 130° C.; crystallizing the devolatilizedpoly(ethylene naphthalate) polymer at a temperature of from about 190°C. to about 205° C.; solid state polymerizing the crystallizedpoly(ethylene naphthalate) polymer at a temperature of from about 240°C. to about 260° C. to form a solid state polymerized poly(ethylenenaphthalate) polymer product.
 18. The product of claim 17 wherein thepoly(ethylene naphthalate) polymer is solid state polymerized at atemperature of 240° C. or more, and the solid state polymerizedpoly(ethylene naphthalate) polymer has a product IV of at least 0.70dl/g and a melting point of less than 270° C.
 19. The product of claim17 wherein the poly(ethylene naphthalate) polymer is solid statepolymerized at a temperature of 250° C. or more, and the solid statepolymerized poly(ethylene naphthalate) polymer has a product IV of atleast 0.70 dl/g and a melting point of less than 275° C.